Abstract
Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z-homoallylic alcohols and amines, respectively.
Highlights
Metal migration through a carbon chain is a versatile method for achieving remote functionalization
Of the available methods for remote functionalization, metal migration through a carbon chain, or “chain walking”, is versatile as it dispenses with the need for complex directing groups (Scheme 1A).[1g–i, 2, 3 ] most known metal chain walking reactions effectively result in the overall net migration of alkylmetal species (Scheme 1A)
During our studies of enantioselective nucleophilic allylations of imines,[4b,5] we discovered the first examples of allylrhodium chain walking (Scheme 1C).[4b]. These reactions employ δtrifluoroboryl α,β-unsaturated esters as precursors to allylrhodium species A
Summary
Metal migration through a carbon chain is a versatile method for achieving remote functionalization. Chain walking of organometallics beyond simple alkylmetals, such as allylmetal species (Scheme 1B), could dramatically expand the scope of remote functionalizations, but to our knowledge, there are such few examples.[4] During our studies of enantioselective nucleophilic allylations of imines,[4b,5] we discovered the first examples of allylrhodium chain walking (Scheme 1C).[4b] These reactions employ δtrifluoroboryl α,β-unsaturated esters as precursors to allylrhodium species A.
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